Review

Biodegradation of Aliphatic and

Aromatic Polycarbonates

Trishul Artham, Mukesh Doble*

Polycarbonate is one of the most widely used engineering plastics because of its superior
physical, chemical, and mechanical properties. Understanding the biodegradation of this
polymer is of great importance to answer the increasing problems in waste management of
this polymer. Aliphatic polycarbonates are known to biodegrade either through the action of
pure enzymes or by bacterial whole cells. Very little information is available that deals with
the biodegradation of aromatic polycarbonates. Biodegradation is governed by different
factors that include polymer characteristics, type of organism, and nature of pretreatment.
The polymer characteristics such as its mobility, tacticity, crystallinity, molecular weight, the
type of functional groups and substituents present in its structure, and plasticizers or additives
added to the polymer all play an important role in its degradation. The carbonate bond in
aliphatic polycarbonates is facile and hence this polymer is easily biodegradable. On the other
hand, bisphenol A polycarbonate contains benzene rings and quaternary carbon atoms which
form bulky and stiff chains that enhance rigidity.
Even though this polycarbonate is amorphous in
nature because of considerable free volume, it is
non-biodegradable since the carbonate bond is
inaccessible to enzymes because of the presence
of bulky phenyl groups on either side. In order to
facilitate the biodegradation of polymers few
pretreatment techniques which include photo-
oxidation, g-irradiation, or use of chemicals have
been tested. Addition of biosurfactants to improve
the interaction between the polymer and the
microorganisms, and blending with natural or
synthetic polymers that degrade easily, can also
enhance the biodegradation.

1. Introduction

Synthetic polymers have come to replace glass, wood,

T. Artham, M. Doble masonry and other constructional materials, and even
Department of Biotechnology, Indian Institute of Technology metals in many industrial, domestic, commercial, and
Madras, Chennai 600036, India environmental applications and their consumption by
Fax: þ91 44 22574102; E-mail: mukeshd@iitm.ac.in 2010 is expected to reach 275 million tons. Until about the

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14 ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/mabi.200700106
Biodegradation of Aliphatic and Aromatic Polycarbonates

Trishul Artham is a Research scholar working

with Prof. Mukesh Doble in the Department of
Biotechnology at IIT Madras, Chennai, India. He
has received his B.Sc (Hons) (2002) and M.Sc
(2004) in chemistry from Satya Sai University,
Andhrapradesh, India. Currently he is working on
biodegradation of polycarbonates as his thesis
problem. His areas of interest include biodegra-
dation of polymers, bioremediation and bio-
transformations.
Mukesh Doble is a Professor in the Department
of Biotechnology at IIT Madras, Chennai, 600036,
India. He has experience in bioreactors, molecular
modelling, drug design, bioremediation/bio-
degradation, homogeneous, heterogeneous and
enzyme catalysis, scale-up, process development,
Figure 1. Structures of a few important aliphatic and aromatic
statistical process control, and six-sigma. He holds
polycarbonates.
B. Tech and M. Tech degrees in Chemical Engin-
eering from IIT, Madras and a Ph. D. from the polymer namely, aliphatics and aromatics. The former are
University of Aston in Birmingham, UK. He has not widely used as thermoplastics but are generally
carried out postdoctoral research at the Univer-
included as comonomers, and the later are known as
sity of Cambridge, U.K., and Texas A&M, U.S.A.
engineering thermoplastics. Amongst the aromatic PCs the
He has previously worked in the ICI and GE
Technology research centers for 20 years in
most important and widely used is poly (bisphenol A
the areas of pharmaceuticals, rubber chemicals, carbonate) (BPAPC).[6]
polymers, explosives, specialty chemicals and
paints. He has authored or coauthored four
1.1. Aliphatic PCs
books, 120 technical papers in international jour-
nals, filed 3 patents and presented in more than These are generally synthesized by: 1) phosgenation of
50 National and International conferences. He is hydroxy compounds, 2) transesterification of diols with
a recipient of Herdillia Award for ‘‘Excellence in lower dialkyl carbonates in the presence of a catalyst, or
Basic Research’’ from the Indian Institute of by 3) ring opening polymerization of six-membered cyclic
Chemical Engineers. He is in the Editorial Board
carbonates. In contrast to aromatic PCs, the aliphatic
of Chemical Engineering and a member of Amer-
PCs are rarely used as thermoplastics. Aliphatic PCs such
ican and Indian Institute of Chemical engineers.
as poly(ethylene carbonate) (PEC), poly(1,3-trimethylene
year 2002 the annual worldwide production of polycarbo- carbonate) (PTC), poly(butylene carbonate) (PBC), and
nate (PC) stood at 2.7 million tons,[1] which rose to around poly(hexamethylene carbonate) (PHC), which have no side
3 million tons in 2006.[2] Its durability, optical clarity, group substituents, are typically synthesized from their
toughness, and ability to be blended with other polymers corresponding cyclic monomers by ring-opening polymer-
are attributes that contribute to its strong performance in ization.[7–9] Poly(ethylene carbonate) is often prepared
recent years (more than 10% growth per year). Apart from from the copolymerization of ethylene oxide and carbon
its applications in automobiles, mobile phones, notebook- dioxide. PCs are more resistant to acid-hydrolysis than
type personal computers, cameras, electric and electronic polyesters. Although the carbonate group is more suscep-
appliances, office equipment, etc, PC is an indispensable tible to base hydrolysis than polyester, the rate of degrada-
resin in the manufacture of CDs and DVDs for music or tion of an aliphatic PC is slower than that of polyester. A
data storage. It is estimated that more than 6 000 billion possible reason for this behavior is the electronegativity
discs of waste was generated worldwide in 2005 alone, differences of the carbon and the three oxygen atoms in
which amounts to more than 5 800 tons of PC in one these two polymers. The carbonyl carbon in PC is more
year.[3] Chemical recycling of PC wastes has gained great electrophilic, compared to the carbonyl carbon atom in
importance during recent years.[3–5] Since this is a short the corresponding polyester. Because of this difference,
term solution, the increasing amount of PC wastes that the carbonyl carbon atom in the PC chain is more suscepti-
come from CDs and plastic objects makes it necessary to ble to attack by hydroxide ions under basic conditions. The
look for a long term solution which is an environmentally consequence is that the PCs do not yield acid groups upon
benign process. degradation unlike polyesters (Figure 2a). The acidic
PC resins can be divided into two structural classes groups that are formed in the polyester catalyze the
(Figure 1) based on their carbon chain backbone in the hydrolysis reaction further.

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Figure 2. Hydrolysis of a) polycaprolactone polyester b) an
aliphatic polycarbonate.
Poly(trimethylene carbonate) can, for example, be used
to prolong in-vivo degradation time.[10] This is probably
because the end group cleaves to liberate CO2 and a hydroxy
group (Figure 2b). PCs are as useful as diols, the later
constitutes the soft segments in polyurethanes. Poly(carbo-
nate diols) bring additional benefits such as increased
hydrolytic stability when compared to polyesters, an
increased thermal stability when compared to polyethers,
and hence provide increased outdoor stability. The increas-
ed hydrolytic stability of the aliphatic PC leads to several
applications, which includes use as resins in coating[11]
and in medical devices and implants.[12]
PC-based polyurethanes (PCNU) have attained popular-
ity in the biomaterials market because of their mechanical
properties, which are similar to conventional polyur-
ethanes, as well as their improved oxidative stability.
Corethane (80A), is a commercially available polycarbo-
nate urethane (PCU) (presently branded as Bionate)
produced under license by Polymer Technology Group,
Berkeley, CA, and is used as an implant material. Several
studies have shown that these materials are more
resistant to oxidative degradation than poly(tetramethyl-
ene oxide) (PTMO), which contains polyurethanes.[13]
1.2. Aromatic PCs
The vast majority of aromatic PCs is based on bisphenol A
(BPA), and are available commercially under the trade
names of Lexan (GE), Makrolon (Bayer), Caliber (Dow),
Panlite (Teijin), and Iupilon (Mitsubishi). In addition, there
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16 ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
T. Artham, M. Doble
are many small-scale manufacturers and suppliers of this
polymer. BPA polycarbonates (BPAPC) have glass transi-
tion temperatures (Tg) in the range of 140–155 8C, and are
widely regarded for their optical clarity, exceptional impact
resistance, and ductility at or below room temperature.
Other properties such as modulus, dielectric strength, and
tensile strength are comparable to other amorphous
thermoplastics at similar temperatures below their respec-
tive Tgs (Table 1). Whereas, most amorphous polymers are
stiff and brittle below their Tgs, PCs retain their ductility.
PCs are prepared commercially by two completely
different processes namely: 1) the Schotten-Baumann
reaction, which consists of an amine-catalyzed interfacial
condensation reaction of phosgene and an aromatic diol,
and 2) base-catalyzed transesterification of a bisphenol
with a monomeric carbonate such as diphenyl carbonate.
BPAPC is a condensation polymer in which benzene rings
and quaternary carbon atoms form bulky stiff molecules,
which promote rigidity, strength, creep resistance and
high heat deflection temperature. The bulky chains
crystallize with great difficulty, so the polymer is normally
amorphous, and has good transparency. The bulky amor-
phous chains produce considerable free volume, which
results in high ductility and impact resistance.[6] The
combination of all these characteristics leads to properties
such as high optical clarity, percent elongation, impact
strength, toughness, heat resistance, and heat deflection
temperature.[14–16] Uses of BPAPC is spread in many areas,
which include construction, electrical, automotive, air-
craft, marine, medical (pumps, connectors, fluid adminis-
tration applications like stopcocks, catheters, syringes,
blood oxygenetaors, and kidney dialyzers), and packaging.
They are also used in household and consumer articles,
baby bottles, water dispensers, sporting goods, photo-
graphy, optical equipment, and laser-optical data-storage
systems.[17] One disadvantage of PC is that it is chemically
attacked by alkalis, amines, and ketones. The same
properties that make the PCs a unique material also pose
serious hurdles in their safe disposal. The solid waste
generated from the usage of PC is a current global concern
since these wastes are not just confined to landfills but are
becoming a major part of marine debris as well. Because of
their increased usage, persistence in the environment, and
because of the increased costs of solid waste disposal
(owing to the reduction in available landfill space), as well
as the potential hazards from waste, it is most important
to address this problem through biological means.
2. Biodegradation
Lack of water solubility and the size of the polymer
molecules, prevents microorganisms from transporting
the material directly into the cells where most biochemical
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Biodegradation of Aliphatic and Aromatic Polycarbonates

Table 1. Properties of polycarbonates.[65]

Property Units Conditions Value

Density g cmS1 ASTM D792 1.20

S1
Intrinsic viscosity dL
g Chloroform at 30 -C 0.5–0.55
Water absorption % At 23 -C 24 h 0.12
Melt flow rate g (10 min)S1 300 -C, 1.2 kgf, 0.5–0.7
Light transmittance % 550 nm 85
Haze % 3
Refractive index STP 1.586
Tensile strength, Type I MPa Yield, break 62.1, 65.5
Tensile elongation, break, Type I % 110
Flexural strength MPa 93.1
Flexural modulus MPa 2 340
Tensile modulus MPa ASTM: D638, D759, D1708 2 380
Yield strain % 6–8
Shear modulus MPa 119
Impact strength J
mS1 Izod, Notched 850
Heat deflection K At 1.8 Mpa 430
Specific heat J gS1 -C 1.67 T 10S3
Continuous use temperature K 373–408
S1
Surface tension mN m 20 -C 42.9
Dielectric constant 60 Hz; 1 MHz 3.17; 2.9

processes take place. Microorganisms can excrete extra-
cellular enzymes that disintegrate the polymers outside
the cells (Figure 3). When the molar mass of the polymers is
sufficiently reduced to generate oligomers and monomers
that are water soluble, these can then be transported
through the semi-permeable outer bacterial membranes,
and hence can be assimilated as a carbon or nitrogen
source through the appropriate metabolic pathway. In
addition, the extracellular enzymes are too large to
penetrate deeply into the polymer material and so can
act only on its surface. Polymers in general, can undergo
degradation either by surface erosion or by bulk ero-
sion.[18] During an application, surface eroding polymers
lose material from the surface only. They become smaller
but keep their original geometric shape. For bulk eroding
polymers, degradation and erosion are not confined to the
surface of the polymer. Therefore, the size of the polymer
will remain constant for a considerable portion of time
during its application. Aliphatic PCs are reported to
undergo surface erosion when used as cage implants
for in-vivo applications.[19–21] The advantage of surface
eroding polymers is the predictability of the erosion
process in drug delivery. Aromatic PCs when exposed to UV
light also undergo surface erosion.[22] In either case the
erosion leads to loss of mechanical properties, decrease in
molecular weight, and morphological changes that lead to
degradation.
When the product evolved during degradation is
primarily a monomer, the process is called depolymeriza-
tion, and if the products evolved are inorganic substances
like carbon dioxide, methane, or water, the process is called
mineralization. The American Society for Testing and
Materials (ASTM) and the International Organization for
Standardization (ISO) define degradation as ‘‘an irrever-
sible process leading to a significant change of the
structure of a material, typically characterized by loss of
properties (e.g., integrity, molecular weight, structure or
mechanical strength) and/or fragmentation. Degradation
is affected by environmental conditions and proceeds over
a period of time comprising of one or more steps’’.[23,24]
Although the enzyme-catalyzed chain length reduction
of polymers is in many cases the primary process of
biodegradation, abiotic chemical and physical processes
can also act on the polymer, either in parallel or as a first
stage in the overall degradation step. These abiotic
processes include chemical hydrolysis, thermal degrada-
tion and oxidation, or scission of the polymer chains by
irradiation (photo-degradation).
There are several factors that influence biodegradation
of polymers (Figure 4). Other than the right microbe,

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 T. Artham, M. Doble

Figure 3. General mechanism of enzyme-catalyzed polymer degradation.

degradation depends on the structure, morphology, and synthetic biodegradable polymers contain hydrolyzable
molecular weight of the polymer. Natural macromolec- linkages such as ester, carbonate, amide, and urethane, in
ules, e.g., proteins, cellulose, and starch, are generally their polymer structure. The introduction of substituents
degraded in biological systems by hydrolysis. Most of the like hydroxy, carboxy, and methyl groups also increase bio-
degradability.[25] Since the
polymer chain must be flexi-
ble to fit into the active site of
the enzymes, flexible alipha-
tic polyesters are much more
biodegradable compared to
rigid aromatic polyesters.[26]
Ease of attachment of the
organism, which is governed
by the hydrophobicity of the
polymer surface, also has an
effect on its degradability.
An additional complicat-
ing factor is the complexity
of the plastic materials with
regard to their possible struc-
tures and compositions. In
many cases commercial plas-
tics do not consist simply
of only one chemically homo-
genous component, but may
contain different polymers
(blends) or low molecular
Figure 4. Parameters that affect the biodegradation of polymers. weight additives (e.g., plasti-

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Biodegradation of Aliphatic and Aromatic Polycarbonates
cizers). Moreover, within one polymer itself, different
structural elements can be present (copolymers), and these
may either be distributed statistically along the polymer
chains (random copolymers), distributed alternately (alter-
nating copolymers), or they may also build longer blocks of
each structure (block copolymers). Another structural
characteristic of a polymer is the possible branching of
the chains or the formation of networks (cross-linked
polymers). These different structures of a polymer, despite
having the same overall composition, can directly
influence its accessibility to the enzyme. A highly ordered
structure of the polymer (crystalline nature) also controls
its nature of degradation. Most of the polymers have short
and regular repeating units with high symmetries and
strong interchain hydrogen bonding that results in highly
and ordered crystalline morphologies thereby limiting the
accessibility to enzyme attack.[27,28] The degradation of
polymers by enzymes is also affected by various para-
meters such as its melting point[29,30] or tacticity.[31] In
solution the viscosity and surface tension of the solvent
influence degradation process.[32,33]
Environmental factors also influence the polymer to be
degraded. They have a crucial role on the microbial
population and on the activity of the different micro-
organisms themselves. Parameters such as humidity, tem-
perature, pH, salinity, the presence or absence of oxygen,
and the supply of different nutrients have important
effects on the microbial degradation of polymers and so
these conditions must be considered when the biodegrad-
ability of plastic is to be tested.
2.1. Biodegradation Studies on Aliphatic PCs
The biodegradation of aliphatic PCs was first investigated
for medical applications. Imai et al.[34] first reported
the biodegradation of poly(ethylene carbonate) (PEC)
implanted in dog tissue and suggested that treatment
with the enzyme pronase might be effective in diminish-
ing the PEC mass. Kawaguchi and co-workers[35] later
reported that PEC was degraded enzymatically in the
peritoneal cavity of the rats, whereas poly(propylene
carbonate) did not degrade. This confirms that the struc-
ture of the polymer plays an important role in the bio-
degradation process. Ethylene glycol was detected during
the Rhizopus delemar lipase catalyzed degradation of PCs
that contain oxyethylene units prepared from epoxides
and carbon dioxide.[9] The weight loss was in close
agreement with those calculated from the yields of ethyl-
ene glycol. Suyama and Tokiwa[36] reported the degrada-
tion of poly(tetramethylene carbonate) (PTC) with the
same enzyme used for the hydrolysis of polyesters. It was
degraded by a cholesterol esterase preparation from
Candida cylindracea; lipoprotein lipase preparation from
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Pseudomonas sp.; and lipase preparation from several
organisms which included C. cylindracea, Chromobacter-
ium viscosum, Pseudomonas sp., and Rhizopus arrhizus.
Tang and co-workers[37] have investigated the influence of
cholesterol esterase activity on the biodegradation of
PCNUs. They observed that the biodegradation was not
dependent on the enzyme concentration when the hard
segment content in the polymer was high it was strongly
dependent on enzyme concentration for polyurethanes
with different types of hard segments. Toshihiro and
co-workers[38] observed that the lipase AK catalyzed bio-
degradation of poly(e-caprolactone) (PCL) sheets decreased
significantly even with small amounts of PC added to it,
because of the more packed structure of PCL in the blend
sheets as compared to the unblended one. Emulsified PEC
and PPC (of Mn 50 000 Da) (Mn ¼ number-average mole-
cular weight) were tested for their biodegradability using
the clear-zone method on an agar. It was found that the
percentage of PEC-degrading microorganisms among the
total colonies ranged from 0.2 to 5.7%. However, no colony
with a clear zone was observed on PPC emulsified plates
even after culturing it for 15 d at 30 8C. Using PEC (of Mn
50 000 Da) as a sole carbon source, a bacterium strain
PC610, was isolated which completely degraded a film of
110 mg in 3 d.[39] Bacteria capable of biodegrading
poly(hexamethylene carbonate) (PHC) was observed to
be able to biodegrade PCL as well.[40] Four bacterial strains,
35L, WFF52, 61A, and 61B2 that could degrade PHC (of Mn
2 000 Da), were isolated from river soil sediments on an
agar plate.[7] All of the PHC-degrading isolates were
phylogenetically diverse, and were classified into beta
and gamma subclasses of the Proteo-bacteria. These
included Duganella zoogloeoides, Psuedomonas lemoignei,
Ralstonia pickettii, Roseateles depolymerans, Variovorax
paradoxus, Acinetobacter calcoaceticus, Acinetobacter
junii, and Pseudomonas veronii. Four of the isolates,
namely Roseateles depolymerans strains 61A and 61B2,
V. paradoxus strain WFF52, and P. veronii strain 35L
formed colonies with clear zones on agar plates that
contained emulsified poly(butylene carbonate) (PBC of Mn
2 000 Da). Furthermore, one strain of a poly(butylene
succinate) (PBS) degrading isolate, Amycolatopsis sp. HT-6,
was also seen to biodegrade high-molecular-weight PBC of
Mn 37 000 Da, as well. A liquid culture that contained
150 mg of a PBC film degraded to 83 mg in 7 d, while only a
small amount of cells was formed.[41]
2.2. Biodegradation Studies on Aromatic PCs
To date there is no open source literature that reports the
microorganism-mediated biodegradation of unblended
aromatic PCs. There are a few studies reported in the litera-
ture that describe the use of PC as a ‘substrate’ for the growth
of biofilms in lakes,[42,43] in drinking water distribution
www.mbs-journal.de 19

system,[44] and in a reverse osmosis process as nano-
filtration membranes,[45] but these studies do not report
any biodegradation. Some authors have made comparison
of biofilm growth on different artificial and natural
substrata; however, their conclusions are contradictory.
Barbiero[46] reported that natural substrata exhibited
greater species richness than artificial ones. Danilov and
Ekelund[47] applied glass slides, glass tubes, pieces of poly-
(vinyl chloride) (PVC), and wood as substrata and con-
cluded that the nature of the substratum can considerably
affect patterns of colonization of algae. Glass tubes turned
out to be the most favorable substratum on the basis of
settlement patterns of algae, while no growth of algae was
observed on PVC pieces. Their results are contradictory to
those summarized by Cattaneo and Amireault,[48] who
concluded that plastics are favorable artificial substratum
for biofilms. Krisztina[49] has used PC for monitoring river
benthic microbiota by growing biofilms on its surface. This
diatom community had a high population of Achnantes
helvetica and the growth was higher on PC than on other
substrates such as plexi glass and polished granite.
The deterioration of polymer surfaces is an interfacial
process and is controlled by the conditions that prevail
directly at these surfaces. If microorganisms are involved
in this process, they initially attach themselves and then
colonize the surfaces in the form of biofilms. Flemming[50]
has pointed out five major ways by which the structure
and function of synthetic polymeric materials can be
damaged by biofilms, which leads to consequences as
listed bellow (Figure 5). They are: 1) masking of the surface
properties of the polymer because of biofilm coating; 2)
increasing the leaching of additives and monomers out of
the polymer matrix during the microbial degradation; 3)
attack by enzymes or radicals of biological origin which
leads to both embrittlement and loss of mechanical
stability; 4) accumulation and penetration of water and
microbial filaments into the polymer matrix, to cause
swelling and increased conductivity, and 5) excretion of
lipophilic microbial pigments that leads to unwanted color
in the polymer.
Figure 5. Schematic representation of biofilm formation on a polymer surface.
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T. Artham, M. Doble
Sivalingam and co-workers[51] have reported the biode-
gradation of bisphenol-A polycarbonate by lipases in
different organic solvents and developed a kinetic model
of the degradation process. They observed that it was
degraded in the solution phase at temperatures that range
from 26 to 70 8C, in solvents such as toluene, tetrahy-
drofuran, and benzene, and by lipases from Candida
rugosa, Hog Pancreas, and Lipolase. They observed that
while the degradation rate decreased with viscosity, it
increased with polarity of the solvents. Lipases are found
to be stable and active in water-immiscible organic
solvents probably because a thin layer of water remains
tightly bound to the enzyme, which acts as a protective
sheath around the hydrophilic surface and thereby allows
it retain its native confirmation and hence its activity.[52]
These desirable properties of lipases make them versatile
in the biodegradation of polymers in organic solvents.
3. Mechanisms of Biodegradation
In nature there are many different degradation mechan-
isms that combine synergistically to degrade polymers.
Microbiological degradation can take place through the
action of enzymes or by the products (such as acids and
peroxides) secreted by microorganisms that include
bacteria, yeasts, fungi, etc. The two major types of degrada-
tion mechanisms are biological oxidation and hydrolysis.
Hydrolysis leads to the formation of low-molecular-weight
oligomers, which are subsequently assimilated by micro-
organisms. Hydrolytic degradation is divided into two
types, catalytic hydrolysis and non-catalytic hydrolysis.
The former degradation process requires enzymes such
as esterases, lipases, and depolymerases, and the latter
requires alkaline metals and solid acids found in the
environment. Because of the presence of the hydrolyz-
able carbonate bond, PCs undergo a hydrolytic-type of
degradation. Oxidation also leads to the molar mass
reduction of polymers. Oxidative scission occurs mainly
because of oxygen, metal, UV light, or by enzymes that
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Biodegradation of Aliphatic and Aromatic Polycarbonates
belong to a class of oxido-reductases. In general, polymers
with a non-hydrolyzable backbone like polyolefins under-
go oxidation.
3.1. Aliphatic PCs
Roseateles depolymerans strains 61A was shown to
degrade PHC to di(6-hydroxyhexyl) carbonate and adipic
acid, and degrade PBC to di(4-hydroxybutyl) carbonate and
succinic acid.[41] Degradation of PBC by lipase from
Pseudomonas sp. produced products such as butane-1,4-
diol, CO2, and di(4-hydroxybutyl) carbonate. Matsumura
and co-workers[53] showed that immobilized lipase CA
from Candida antarctica (Novozyme 435) at 70 8C and in an
organic solvent, could convert poly(trimethylene carbo-
nate) (PTMC) to the cyclic trimethylene carbonate. Stoll
and co-workers[54] have observed the formation of cyclic
trimethylene carbonate during the in-vivo degradation of
PEC used as an implant. They have proposed a mechanism
that involves the attack of a superoxide anion radical[55] on
PEC to form ethylene carbonate by cyclization (Figure 6).
Several systematic studies have been reported on the
influence of esterase[37] on PCNUs, and the effect of
structure[56] and morphology[57] of this polymer on its
biodegradation. The study focused on the influence of
different hard segment structures on the rate of enzyme
catalyzed hydrolysis. The study concluded that the bio-
degradation was initiated in the amorphous soft segment
regions located in the interface between the hard and soft
segments. A higher fraction of hard segment at the surface
contributed significantly to an increase in its biostability.
When this investigation was carried out at the molecular
level, it was found that the degree of phase separation and
the soft segment crystallinity were less important in
comparison to the extent of hydrogen bonding amongst
Figure 6. Mechanism for PEC in vivo degradation.
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the carbonate and urethane linkages. The susceptibility
of the different chemical groups to hydrolysis was as
follows starting from the most to the least susceptible:
non-hydrogen bonded carbonate > non-hydrogen bonded
urethane > hydrogen bonded carbonate > hydrogen bonded
urethane. The findings suggest the importance of the degree
of hydrogen bonding, the role of surface molecular
structure, and a strong dependence on enzyme concentra-
tion. These parameters need to be kept in mind while
designing new biostable polymeric products.
3.2. Aromatic PCs
Aromatic PCs, which are of great technical relevance
because of their excellent material properties, undergo no
appreciable hydrolysis at physiological temperature and
pH or with increased amounts of enzymes. Enzymes that
are known to catalyze carbonate bonds are also few. An
article on the biodegradation of polyesters by Muller[58]
throws light on why aromatic polyesters do not undergo
biodegradation at rates comparable to aliphatic polyesters.
The necessity of the long polymer chains to penetrate into
the active site of the hydrolases, which is often located in
a deep cavity of the enzyme, makes the mobility and
flexibility of the polymer chains the most important factor
that controls its degradability. Since this mobility is
correlated with the melting point of the material, and
BPAPC is a high melting polymer, it can be concluded that
it is unlikely to be degraded at a reasonable rate. There are
no reports on the biological oxidation of BPAPC.
Albertsson and Anderson[59] has described the mechan-
ism of biodegradation for polyethylene assuming an initial
photo-oxidation step. Hence it could be assumed that
biotic degradation of BPAPC can also possibly be preceded
by a photo-oxidation step. The photodegradation of PC
occurs by a photolytic pathway when it is directly excited
by wavelengths absorbed by the chromophoric groups of
aromatic PC. This mechanism is generally believed to be
initiated by wavelengths shorter than about 310 nm.
Direct scission of one of the C –O bonds of the carbonate
group leads to the formation of two free radicals. The
subsequent Photo-Fries rearrangement produces a poly-
meric phenyl salicylate-type of structure (Figure 7a). In the
presence of oxygen, some of the radicals undergo typical
photo-oxidation chain reactions, which lead to formation of
peroxy radicals that abstract hydrogen atoms from the
macromolecular chain to form hydroperoxides (Figure 7b).[60]
4. Enhancement of Biodegradation
Several physical and chemical pretreatment techniques
have been reported to enhance the biodegradation of
polymers. The success of the pretreatment technique
www.mbs-journal.de 21
 T. Artham, M. Doble

depends on the type of polymer.

Although no pretreatment tech-
nique has been reported to enhance
the biodegradation of PC, a few
techniques that appear to be pro-
mising are listed below. Photolysis
with UV light or g-ray irradiation of
polymers generates radicals and/or
ions that often lead to the cleavage
of bonds and cross-linking between
various chains. This leads to an
increase in network density, which
is an obstacle during the swelling
and dissolution of the polymer. It
also prevents the access of the
bacteria to its carbon source.[61]
Presence of oxygen during UV
irradiation will lead to more com-
plicated reactions between the radi-
cals formed and molecular oxygen.
Generally this improves the materi-
als susceptibility to biodegradation.
Initially, one expects the observed
rate of UV degradation to increase
until most of the fragmented poly-
mer is consumed. This could be
followed by a slower rate of degra-
dation when the attack is on a
cross-linked portion of the polymer.
The degradation of BPAPC by
g-irradiation has been reported ear-
lier.[62] Bacterial adhesion, which is a
primary step in the biodegradation
process, is affected by the surface
hydrophobicity. Generally PCs are
more polar when compared to
polyolefins because of the presence
of hetero atoms in the backbone of
the polymer. Increasing the hydro-
philicity of the polymer surface by
chemical modifications such as
alkali or amine[63] treatment pro-
motes its biodegradability since
the organisms can readily attach
themselves to the surface. Another
way to enhance the bacterial
adhesion (biofilm) would be to
add biosurfactants. This would
decrease the surface tension be-
tween the bacterial cell wall and
polymer surface, which leads to
increased biofilm growth and sub-
sequent biodegradation. Biosur-
Figure 7. a) Photo-oxidation of BPAPC. b) Gemdimethyl side-chain photo-oxidation of PC. factants added to hydrocarbons is

Macromol. Biosci. 2008, 8, 14–24

22 ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/mabi.200700106
Biodegradation of Aliphatic and Aromatic Polycarbonates
found to improve their bioavailability to the microbial
cells by increasing the area at the water–hydrocarbon
interface. This increases the rate of hydrocarbon dissolu-
tion and their utilization by microorganisms.[64] The use of
polymer blends is one more approach to increase the
biodegradation but it has its own drawbacks. One ends up
by compromising on the material properties by blending
the original polymer with other polymers. For example,
bisphenol A polycarbonate is known for its optical clarity
and toughness but is non-biodegradable. In order to
degrade this polymer, it can be blended with an aliphatic
PC like PHC, which is known to easily biologically degrade.
But the material properties of the BPAPC might change
drastically since PHC is not a thermoplastic.
5. Conclusion
In general, aliphatic PCs are known to biodegrade at a
faster rate than aromatic PCs. The biodegradation of PCs is
governed by different factors that include environmental
as well as bulk and surface properties of the polymer. The
necessity of the polymer chain to penetrate into the active
site of the enzyme makes the mobility of the polymer an
important parameter that controls the degradation
process. Reports on lipase-catalyzed degradation of PC in
organic solvents supports the fact that accessibility of
the polymer to the enzyme is the limiting factor. Since
the hydrophobic domains in lipases are more open and
accessible in organic solvents such as toluene, as opposed
to water, it could be assumed that the carbonate bonds in
the vicinity of bulky aromatic groups are more accessible
for the lipases to hydrolyze in organic solvents without
much steric hindrance. No literature reports have been
found that mention the biodegradation of BPAPC. Since the
Figure 8. Various approaches for enhancing biodegradation of
BPAPC.
Macromol. Biosci. 2008, 8, 14–24
ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
mobility of the polymer is correlated to its melting point,
and BPAPC has a high melting temperature, it could be
presumed that its rate of degradation is poor.
Isolating the correct microorganism is also an important
factor. Microbes under stress should either be able to
express the necessary enzymes for the degradation of the
polymer, or should produce surface active compounds like
biosurfactants to reduce the surface tension between the
polymer and microorganism so that the latter can attach
itself on to the polymer surface to form a biofilm. The PC
can be degraded biologically if it is either pretreated with
g-irradiation, thermally treated above 350 8C, or photo-
oxidized by exposing it to UV irradiation and then fed as a
carbon source to the microorganisms. The above said
pretreatment processes would initiate the degradation
and reduce the molecular weight of the polymer so that
microbes can assimilate them more easily. Figure 8
summarizes the various possible techniques for enhancing
the biodegradation of PC, more specifically aromatic PCs.
Received: April 26, 2007; Revised: July 18, 2007; Accepted: July 26,
2007; DOI: 10.1002/mabi.200700106
Keywords: biodegradable; lipases; polycarbonates; pretreatment
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24 ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/mabi.200700106